Adsorption method for separating thorium values from uranium values



vrnat'ographic adsorption techniques.

United States Patent ABSORPTION METHOD FOR SEPARATING THO- RIUM VALUES URANIUM VALUES George Boyd, Oak Ridge, Tenn., and Edwin R. Russell and Jack Schubert, Chicago, Ill., assignors to the i United states of America as represented by Y States Atomic Energy Commission v No Drawing. Application September 14, 1949 Serial No. 115,778.

the United nium is also always contaminated with thorium since various thorium isotopes are natural decay products of the uranium isotopes found in nature. 'For example, UXfl Th is continually produced by the radioactive decay otthetLTi? isotope "as shown by the following schemes,

. DZ s0 1,) o1 2) v I t 4.51 10 V '24.5d a e The purified radioactive thorium isotopes which may be isotopes, UXi being particularly valuable'because of its relatively short half-life.

An' object of the present invention is toprovide a method for the'separation of thorium values from aqueoussolution, and for the concentration of said thorium values. V

A further object ofjthe present invention is 'to provide a method of separating thorium valuesfrom uranium values, particularly where the thorium is present in very small concentration with respect to the uranium.

Still other objects will beapparent from the .following detailed description.

s .In accordance with the present inventionit has been found that thorium values may be readily and quantitatively separated from an. aqueous solution by the adsorption of thorium ions upon a suitable adsorbent. Substantial' concentration of the thorium values can .then be obtained bydesorbing the thorium with a small quantity of an aqueous solution, It has fiurther been found that thorium values can be separated from nraniumivalues even when thethoriumivalnes are: in very minute fcon centration with reference to the uranium values by the selective adsorption and desorption of said thorium values .With suitable adsorbents. This process may be particularly advantageously) carried out by making use o f. chr o- The preferred-embodiment. of the present invention comprises broadly the treating of an adsorbenb'preferably of the cation exchange resin type, with aqueous solution containing ionic thorium and uranium values whereby the thorium ionsarepreferentially adsorbed thereon resulting in the substantially complete adsorption of' the thorium values and, the adsorption of lesser pen 'centagesw of the uranium, ionsfi lfhe *adso 'br dyuranium values are then 'removedfrom the adsorbentby passing an: aqueous diliu'te acid solution in contact withthead} s orbent. Thisresults in a separa'tion, otthe thorium values fromfthe uranium values. Followingjth "desorpti' fiO the'uranium values, the thorium values n then'be're .1

, 2,898,185 Patented Aug. 4,. 1959 solution, preferably containing ions which will form a thorium complex, through the bed. The process of the present invention depends upon the extremely strong adsorption aflinity of thorium for certain adsorbents, an aifinity which is much greater than that of the uranium ions. 'The process of the present invention will effect a separation of thorium from uranium even when'the thorium is present in very dilute concentration with respect tothe uranium concentration, for example, less than 10- M thorium in an 0.1-1 M uranyl nitratesolution.

While it is contemplated that the process of this in vention may be carried out with any adsorbent having an affinityfor ionic species of thorium and uranium, in cluding both inorganic adsorbents, such as silica gel, alumina, diatomaceous earth and the like, and organic adsorbents, such as activated carbon, sulfonated carbonaceous material and the like, it has' been found that the cation exchange resins are particularly suitable adsorbents for use in this process. Examples of suitable resins include the phenol formaldehyde polymers containing free methylene sulfonic acid, carboxyl and phenolic groups described in U.S. Patents 2,104,501 (January 4,1948), 2,151,883 (March 28, 1938), and 2,191,853 (February 27, 1940),'and the cross-linked aromatic hydrocarbon polymeric resins containing nuclear sulfonic acid groups i 7 that in a column adsorption the 40-100 mesh sizes give obtained from natural uranium have wide uses as tracer the most desirable results. While the hydrogen type of resin is normally used, the cation of the prepared resin may be any cation having a lesser aflinity for the resin than thorium. Thus, suitable resins include the uranyl, sodium, potassium and ammonium types.

There are various methods wellknown in the art of contacting adsorbents with solutions containing ionic species to bring about adsorption of the ionic species therefrom. The batch methodis. one of these methods which may be used in the present invention. This method comprises bringing the adsorbent into contact with an aqueous solution containingthe thorium and uranium species. The thorium species will be preferentially adsorbed upon the adsorbent. The adsorbent then may be separated from'the solution by any of the conventional methods of separating solids from. liquids, such as cena trifugation, filtration, .etc., and the uranium separated trom the adsorbent by contacting the adsorbent with a suitable solution which will desorb the less tightly bound uranium but leave the thorium upon the adsorbent. The thorium may then be recovered from the adsorbent. by contacting the adsorbent with a solution which will de; sorb the thorium. v

In a variant of the batch method, the adsorptive capacity of the particular resin used for thorium is first determined. '.The' quantitylof thorium contained in the thorium-uranium solution is analyzed; The solution, preferably containing less than "10 7 M thorium ions andbetween .Q.1-1.;UO "f'. ions, is then contacted with a quantity of resin sufiicient to adsorb the thorium but insufiicient to adsorball of the uranium. This method icovered'froni the adsorbent by passing ad-aqueous acidic depends upon the fact that thorium has a much greater 'afilnity for the .resin than the uranium ions. e The generallypreferredmethodfor adsorbing and do;

A sorbing ionic species from solution is'the column. method also lcnown as chromatographic.adsorption, By this method, the adsorbent is packed into a cylindrical column the solution containing the ionic: species to' be adsorbed is passed through theadsorbeiitflbed"in e' column. Where two or mores ubstaiices having diitefent strengths of attraction for the adsorbent are contained substances to be adsorbed in strata or layers. The layers of adsorbate having higher adsorption aflinity will, in the caseof downwardflow of solution through the column, be. above thelayer of .adso'rbateshaving lower adsorption. affinity; thus, in the case of a downward flow of a solution containing ionic values of thorium and uranium, 'thethorium willbe adsorbed in a separate bed-from the uranium, said thorium bed'lying above the uranium adsorption zone. Since the adsorbed ions of the twospecies will lie in separate zones, the mere passing of a solution containing ions of these two species through an adsorbent column 'bed will result'in a separation of the two species. It isnearly always desirable to obtain the speciesin separate solutions, however, and there are, in general, three methods of doing" this. i The 'first'method, and the one originally used in chromatographic adsorption, was the physical separation of the layers of resin containing. the adsorbed substances and then separately contacting the resin .layers with a Idesorbentfor the particular species adsorbed thereon. The second method depends upon the fact that adsorption and desorption of the ionic species on the adsorbent is an equilibrium process. By this method, the original solution containing the ionic values or asimilar solution is passedfor a considerable length of time through the adsorbent bed. The continued passageof the solution results in the continuous. adsorption and desorption of the separate'layersof adsorbed substances so. that these layers become progressively lowered in the case of downward'flow of the solution in the column. By this progressive lowering of the adsorbed strata, the adsorbed species will eventually pass out of the column in theeffluent solution in separate portions thereof, thus making it possible to obtaineflluent portions containingthe individual species desired.

.The third and most efiicient method of removing the adsorbed species is the method of using selective eluants. By this method, the first solution introduced is selected so that it will remove the ionic species having the lesser afiinity for the adsorbent with the least possible movement of the adsorbent zone .of the ionic specieshaving the greater adsorptiveafiinity. The second solution introduced in the columnis one selected to. remove the more tightly. bound adsorbed ionic species'in the smallest possible. quantity of solution. Thus, in. the case of thorium and uranium adsorbedlayers with the uranium layer lying below the thorium layer in the column, the first solution usually comprises a dilute acid in a quantity sufficient to remove substantially all of the uranium butinsufiicient to remove any substantial amount of the adsorbed thorium from the column. This quantity Willdepend upon the eluant used, .the type of resin and the amount of adsorbed uranium, but may readily be determined in practice by analyzing a portion of the efiluent to determine when the uranium desorptionceases. Since the uranium is more easily dissolved from the resin and since the uranium layer lies below the thorium layer in the column, this may usually be accomplished with. a minimum of downward movement of the thorium layer in .the column and with very little of the thorium being removed with the uranium efiluent solution. The second solution is then passed through the column to remove the thorium. The thorium eluant may be a solution of the-same kind as that used to remove the uranium but it is usually selected so. that itcontains ions with .a complexingefiect upon the adsorbed thorium ions. Thiswill result in a more rapid removal of the adsorbedthorium ions, permitting the use of a smaller amount of eluant and resultingv in a higher thorium concentration in' the eluate. i

The influent solution in the adsorption step of the processof this invention shouldbe an aqueous solution containing thorium and uranium ions; .dilute solutions of strong mineral acids, such asnitric acid, hydrochloric acid and sulfuric acid, .are often used. Equally satisfacory sq u s. ho e aye p e a e yd s lving l t "t I um' i ope, UX1(9' Th resin' is referred to as UO R suitable soluble thorium and uranium salts in water.

The pH is usually maintained on the acid side to avoid formation of insoluble hydroxides. In a solution containing thorium ions, it is probable that there is a mixture of ionic species such as Th+ .Th(OH) Th0+ and Th(OH) Except in highly acid solutions, the predominantcationsare probably 'ThO+ and 'Th(OH) with the relative ratio of the two depending upon the acid concen tration. There are probably similar variantsv of the uranium ionic species-with the U0 species' probably predominating. The mostefficient' adsorption of the thorium is obtained "from .dilute solutions of the thorium ions. Thus, where a resin of the sulfonated phenol-formaldehyde type is usedas'the adsorbent, nearly adsorption of the thorium will be obtained where the thorium is present in concentrationof'l0- M or less. This figure is based upon the use of a minimum amount of resin in the batch method. The maximum adsorptive capacity of the aboveresin is of theorider .of 1.7 milliequivalents. of thorium per gram of bone dry resin. vA maximum adsorptionof the thorium from solutions of much higher concentration may, of course, .beobtained where the column adsorptionmethod involving an. excessamount of resin is used. .Ithas also been found desirable to maintain the uranylconcentration infthe adsorption step influent to-less than. aboutl M in order to obtain the most efficient adsorption with the. amount of resin.

.Thesolutionsusedto desorb the'adsorbed substances from the adsorbent may be any solution containing cations exchangeable for the ions to be desorbed. The

term eluan will be used to describe the influent solu-' tion in the desorption step of this process, and the term eluate will be used to describe the eflluent solution in thedesorption step. The preferred eluant for uranium is a'dilute aqueous solution of a strong acid preferably one having an anion with which thorium does not form a complex ion. Dilute solutions of nitric acid, sulfuric acid and hydrochloric acid may be used arid a 0.1-0.4 M sulfuric acid solution has been-found to be very satisfactory with a 0.25 IM sulfuric acid solution preferable. Aqueous solutions of acid-forming salts and the like in varying concentrations may also be used. The thorium eluant may be the same solution as is used for removal of the uranium with the exchangeable cation present either in the same or in greater concentration. Solutions, which have been found particularly effective in thorium removal because of the complexing elfect of the anions present in the solution, are an approximately 1.25 M NaHSO solution and an approximately 0.5 M H C O solution. The last solution isvery often used where the thorium is present in very smallor tracer. concentrations such as 10- M or less. Where the thorium is present in tracer concentrations and theoxalicacid eluant is used, the thorium may be further concentratedby adding sufiicient inactive thorium ion to theeluate: to .cause a precipitation of thorium oxalate. This thorium oxalate precipitate may then-be separated from. thesolution and dissolved in a small volume of 8 N HNO A concentrationfactor of 200 may be realized by this. additional. step.

.Now. that the process of this invention has been broadly described, specific applications may be further illustrated by the. following. examples. .The first example describes the result of. experiments in which the batch method was used .to separate thorium from aqueous solutions using a cation exchange resinasan adsorbent.

EXAMPLE I [Theadsorbent used was a cation exchange resin of the methylene sulfonic acid type and was prepared by replacing the cation of the resin with uranyl ion. The prepared A specific amount of the resin was then introduced into a measured volume of a uranyl nitrate solution containing specified amounts of The concentrations t n a s i resh w pa 1 of th l ll i s solution in contact with the resin tov permit substantially complete adsorption ofthe thorium, and the resin was then separated and the solution and resin analyzed by 6 What is claimed is: i 1. A methodof separating thorium ions from uranium ions in an aqueous solution containing ions of uranyl uranium and ions of thorium, which comprises contacting radiometric and gravimetric methods, and the results are 8 said solution with a cation'exchange resin in an amount shown in part III Of the table. The percentages of sufiicient to adsorb substantially all of the thorium ions thorium adsorbed are shown in part IV of the table. but insufiicient to adsorb all of the uranium ions and Table l i I II III IV Initial concentrations of adsorbent and ionic species by Final concentrations by analysis, moles/liter Wt. of alrdried analysis, moles/liter 1 Percent resin, g. h

, adsorbed Th Th Th solid UOr UOZRfl solution U01" UOzRs solution (by difference) 0.22 0.017 1 x 0.22 0.017 1.5 X 10- .98 X 10- 98.5 .22 .017 1 x 10- .22 .017 1. 5 x 10- .98 x 10- 98.5

22 .017 1 x 10- .22 .017 2.0 x 10- .98 10- 9s 22 .017 1 x 10- .22 .0168 2. 6 x 10- .97 x 10- 97. 4 22 .017 1 x 10- .222 (.015) 5. 0 x 10- .95 x 10- 94. 9

1 Volume of solution in all cases was 50 ml. The solid phase components UOzR: and Th solid are treated as though they existed independentlyin solution and the concentrations are therefore expressed as moles/liter.

It is to be understood that the foregoing experiments separating the solution containing unadsorbed uranium were carried out with a specific resin using the batch method and for the purpose of finding the variables using a minimum quantity of resin. Therefore, the variables shown are not to be considered as limitations upon the separation of thorium' and uranium where a column adsorption method is used or where more than the minimum quantity of resin in relation to the amount of thorium to be adsorbed is used, since an increased quantity of resin will permit a much broader variation of the variables shown above.

The process of this invention may be further illustrated by the following example showing the separation of UX from natural uranium by the column method using selective eluants.

EXAMPLE II A column that consisted of a glass tube 50 in. long and 1 in. in diameter was filled to a depth of 36 in. with a synthetic organic cation exchange resin of the sulfonated phenol-formaldehyde type. The resin was converted to the acid type by passing 3 l. of 6 N H 80 through the colunm at a rate of about 40 cc./min. Three liters of distilled water was then passed through the column to remove any residual H 80 Five liters of 1 M uranyl nitrate hexahydrate (UNH) was next passed through the column. The 5 l. of the UNH solution contained 839x10 disintegrations per minute of Th (UX which is equivalent to 6.82 10" moles of UX The uranyl ions adsorbed upon the column were removed from the column with approximately 6 l. of 0.6 N H 80 and the column then washed with 2 l. of distilled water. The thorium was recovered from the column by passing 4 l. of 0.5 M oxalic acid through the column. The thorium contained in this wash solution was then concentrated by evaporating the 41. of the solution to 2 l. and then adding 50 mg. of thorium (as the nitrate) with stirring whereby a thorium oxalate precipitate was formed. The precipitate was allowed to setfle and the supernatant then decanted off. The slurry remaining was centrifuged and the thorium oxalate was dissolved in 5 ml. of hot concentrated nitric acid. 'The thorium separated by this method amounted to 4.80 l0 disintegrations per minute, a percentage yield of 57.3%.

The above detailed description has been presented for illustration and the invention is to be limited only by the scope of the following claims.

ions from the cation exchange resin containing thorium values.

2.. A method of separating thorium ions and uranium ions in an aqueous mineral acid solution containing less than 10'" M concentration of thorium ions and between 0.1 and 1 M concentration of uranyl uranium ions, which comprises contacting said solution with a sulfonated phenol-formaldehyde cation exchange resin in an amount not substantially greater than 1 g. dry resin per 1.7 milliequivalents of thorium present whereby substantially all of the thorium ions present are adsorbed leaving a substantial portion of the uranium ions in solution and separating said resin containing adsorbed thorium values from the solution.

3. A method of separating values of thorium and values of uranium, which comprises forming an aqueous mineral acid solution containing thorium ions and uranyl ions, flowing said solution through a column containing a cation exchange resin adsorbent whereby substantially all of the thorium values and a portion of the uranium values are adsorbed on the adsorbent, desorbing said adsorbed uranium values by flowing a dilute aqueous mineral acid solution through the column until substantially all adsorbed uranium values are desorbed, and desorbing said adsorbed thorium values by passing a dilute aqueous acidic solution containing a weakly acidic thorium complexing agent of the class consisting of oxalate and bisulfate ions.

4. The process of claim 3 wherein the adsorbent is a resin of the phenol-formaldehyde polymeric type containing free methylene sulfonic acid, carboxyl and phenolic groups.

5. The process of claim 3 wherein the adsorbent is a cross-linked aromatic hydrocarbon polymeric resin containing nuclear sulfonic acid groups.

6. The process of claim 3 wherein the uranium eluant is a 0.25 M H 50 solution.

7. The process of claim 3 wherein the thorium eluant is a 0.5 M H C O solution.

8. The process of claim 3 wherein the thorium eluant is a 1.25 M HSO; eluant.

9. A method of separating thorium from uranium values present in a solution containing less than 10" M thorium ions and between 0.1 and 1 M uranyl ions, which comprises flowing said solution through a column con- 7 taining phenolformaldehyde type resin whereby substanxReferences Ci tecl i rl the file of this;v patent tially all of; the thorium ionsareadsorbedthereon-and at Tompkins a1: ylloh rExahange as Separations least a portion of the uranium 10118 816 adsorbed thereon, Method, Journal of American. Chemical, Society, flowing a uranium eluant that isbetween 0.1 and 0.4M 69 Pages 17 9:2777 1947 i in Sulfuric acid through i Column whereby afleast 5 Speddi-ng-et aL-fThe'Separation-of Rare-Earths by Ion a portion of the adsorbed uranyl ions arefiesorbedafld Exchange, Journal ofthe "AmeIican-Ghemical Society, collecting said desorbeduranyl ions as a substantially vol. 69,"pages 2777-2781 (1947); V 7 separate fraction, passing a thorium eluant that is ap- Marinsky et al.: The Chemical Identification of Radioproximately ()5 M i H C O through id column 10 isotopes of Neodymium and of Element 61, Journal of whereby at least a portion of the thorium ions are dethe Amman-chemwal 3, Pages 2781" sorbed and collecting said thoriummontaining. portions as 2785- a substantially separate fraction. 

1. A METHOD OF SEPARATING THORIUM IONS FORM URANIUM IONS IN AN AQUEOUS SOLUTION CONTAINING IONS OF URANYL URANIUM AND IONS OF THORIUM, WHICH COMPRISES CONTACTING SAID SOLUTION WITH A CATION EXCHANGE RESIN IN AN AMOUNT SUFFICIENT TO OBSORB SUBSTANTIALLY ALL OF THE THORIUM IONS BUT INSUFFICIENT TO ADSORB ALL OF THE THORIUM IONS AND SEPARATING THE SOLUTION CONTAINING UNADSORBED URANIUM IONS FROM THE CATION EXCHANGE RESIN CONTAINING THORIUM VALUES. 